CN101479408A - Electrochemical reactor - Google Patents
Electrochemical reactor Download PDFInfo
- Publication number
- CN101479408A CN101479408A CNA2007800236239A CN200780023623A CN101479408A CN 101479408 A CN101479408 A CN 101479408A CN A2007800236239 A CNA2007800236239 A CN A2007800236239A CN 200780023623 A CN200780023623 A CN 200780023623A CN 101479408 A CN101479408 A CN 101479408A
- Authority
- CN
- China
- Prior art keywords
- reactor
- bed
- saccharoid
- aforementioned
- grid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000975 dye Substances 0.000 claims abstract description 96
- 238000000034 method Methods 0.000 claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 55
- 230000009467 reduction Effects 0.000 claims description 53
- 230000008569 process Effects 0.000 claims description 35
- 239000000049 pigment Substances 0.000 claims description 25
- 238000004043 dyeing Methods 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 230000005484 gravity Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004061 bleaching Methods 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000010924 continuous production Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 239000013528 metallic particle Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 abstract description 26
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000011144 upstream manufacturing Methods 0.000 abstract description 2
- 239000000984 vat dye Substances 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000000243 solution Substances 0.000 description 26
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 22
- 229940097275 indigo Drugs 0.000 description 22
- 230000002829 reductive effect Effects 0.000 description 22
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004040 coloring Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000007868 Raney catalyst Substances 0.000 description 5
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- RFSUNEUAIZKAJO-VRPWFDPXSA-N D-Fructose Natural products OC[C@H]1OC(O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-VRPWFDPXSA-N 0.000 description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- 229930195725 Mannitol Natural products 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- CMSRLFLXFXUENW-UHFFFAOYSA-L disodium;2-(3-oxido-1h-indol-2-yl)-1h-indol-3-olate Chemical compound [Na+].[Na+].N1C2=CC=CC=C2C([O-])=C1C1=C([O-])C2=CC=CC=C2N1 CMSRLFLXFXUENW-UHFFFAOYSA-L 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000594 mannitol Substances 0.000 description 3
- 235000010355 mannitol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- -1 thiourea peroxide Chemical class 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 108020000290 Mannitol dehydrogenase Proteins 0.000 description 2
- BAWFJGJZGIEFAR-NNYOXOHSSA-O NAD(+) Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 BAWFJGJZGIEFAR-NNYOXOHSSA-O 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 2
- 239000003657 drainage water Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 description 2
- BOPGDPNILDQYTO-NNYOXOHSSA-N nicotinamide-adenine dinucleotide Chemical compound C1=CCC(C(=O)N)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]2[C@H]([C@@H](O)[C@@H](O2)N2C3=NC=NC(N)=C3N=C2)O)O1 BOPGDPNILDQYTO-NNYOXOHSSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002953 phosphate buffered saline Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PGYZAKRTYUHXRA-UHFFFAOYSA-N 2,10-dinitro-12h-[1,4]benzothiazino[3,2-b]phenothiazin-3-one Chemical compound S1C2=CC(=O)C([N+]([O-])=O)=CC2=NC2=C1C=C1SC3=CC=C([N+](=O)[O-])C=C3NC1=C2 PGYZAKRTYUHXRA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910000545 Nickel–aluminium alloy Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010014 continuous dyeing Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002083 enediols Chemical class 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- UMTMDKJVZSXFNJ-UHFFFAOYSA-N nickel;trihydrate Chemical compound O.O.O.[Ni] UMTMDKJVZSXFNJ-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1021—Electrochemical processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/40—Cells or assemblies of cells comprising electrodes made of particles; Assemblies of constructional parts thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/002—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least an electrode made of particles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
- D06B23/20—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration or distillation
- D06B23/205—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration or distillation for adding or mixing constituents of the treating material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
- D06P1/221—Reducing systems; Reducing catalysts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
- D06P1/222—Oxidising agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
- D06P1/228—Indigo
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/30—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using sulfur dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/20—Physical treatments affecting dyeing, e.g. ultrasonic or electric
- D06P5/2016—Application of electric energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Hybrid Cells (AREA)
Abstract
The disclosure pertains to an electrochemical reactor (1), in particular but not exclusively for vatting sulphur dye or vat dye as well as to methods of using such a reactor and to uses of such a reactor. The electrochemical reactor comprises at least one liquid compartment (3) in which a multitude of freely suspended granules (14) is enclosed, wherein at least one of the side walls (5) of the compartment is an electrode and an opposite side wall is formed by a separator element (6), typically a membrane (6), wherein there is provided a bottom inlet (7, 9) and a top outlet (8, 10) of the compartment for a liquid catholyte (9) or a liquid anolyte (7), wherein the inlet region as well as the outlet region of the compartment (3) are provided with an upper grid (11') and a lower grid (11''), the width of the mesh and the positioning of which is chosen such as to allow the liquid catholyte or the liquid anolyte to pass through from bottom to top but to prevent the granules to pass through the grids to leave the compartment, and wherein the upstream flow of the liquid catholyte or of the liquid anolyte can be adjusted so that in operation the multitude of granules is dragged against the upper grid while the lower grid is substantially not in contact with the granules.
Description
Technical field
The disclosure relate to particularly but not only be used for thioxine dyes or vat pigment vatting (vatting) the electrochemical reactor field and relate to the method for using this class reactor and the purposes of this class reactor.
Background technology
Up to now, vat pigment and the thioxine dyes purposes that is used for textile fibres printing and dyeing still is accompanied by using of the excessive reductive agent of stoichiometry (for amount of dye to be restored).The reduction of vat pigment usually occurs in the reductive agent that contains V-Brite B (vat powder) or be derived from it, and (RONGALIT C for example is BASF) and in the alkalescence of wetting agent and complexing agent (pH〉9) aqueous solution.
The redox-potential of reductive reductive agent under the required condition of reducing dyes that is fit to vat pigment be-400mV arrives-1000mV.The using of hyposulfite and thiourea peroxide all causes the carrying capacity height of sulphite in the drainage water or vitriol.These salt of institute's load are poisonous on the one hand, have corrodibility on the other hand and cause the breakage of concrete duct etc.Another problem of vitriol load of sulphite of resulting from the drainage water is to cause the formation of hydrogen sulfide in the sink drainage pipeline because of anaerobe.
Equally, newer method only can partly solve mentioned problem.Here, utilize ultrasonic reactor to be worth mentioning in conjunction with the reduction of conventional reduction agent.This method has that stoichiometric ratio is reduced in reductive agent consumption and hyposulfite can be by enediol alternate advantage.A kind of known electrochemical method uses hyposulfite, produces other reducing dyes reaction product by hyposulfite, thereby reduces the required hyposulfite amount of reducing dyes.
In addition, by WO 90/15182 known a kind of method of carrying out electrochemical reduction by means of medium (mediator).Described medium is the reversible redox system, as makes reducing dyes and at the continuous regenerated iron of negative electrode (II/III) complex compound.Still there are sharp-pointed environmental problem in high consumption and ecological seriousness based on this class medium, and this environmental problem can only solve by additional investment in suitable waster water process or by working cycle.Another shortcoming of this method is: need supply with extra medium incessantly for keeping oxidation reduction cycle in continuous dyeing process.The extra dosing of medium system is the result of the liquid discharge that is directly proportional with fabric or yarn flow.
At mentioned problem, produced a kind of new solution, this method is the reducing dyes that allows no reductive agent in itself.What for example proposed to need not extra reductive agent among the WO 00/31334 in the continuous operation mode process of reactor begins the electrochemical reduction that mechanism is carried out according to difference.
Mentioned electrochemical method (WO 90/15182 and WO 00/31334) common shortcoming is that the reactor specific power is limited, must provide very large electrode surface for improving specific power.
A kind of existing method has been described among the WO 94/23114, wherein use the indigo white textile material dyeing that comes for cellulose of producing by catalytic hydrogenation, and in dyeing course in the dye liquor by the air contact oxidized indigo white part by using the medium system by electrochemical reduction.Indigo white be absorbed in the textile material after, dyeing takes place in a usual manner.Therefore, this method above-mentioned shortcoming of being similarly the medium technology perplexs.
As in the prior art, for the needs of high transforming factor fast restore use solubilizing agent, in fact distribute to apply in particular for the substantially all even particulate that generates dyestuff ultrasonicly can cause the very large pressure-losses and stop up as the electrode that strainer forms.
This method of electric catalyticing hydro of nickel or similar big surface conduction catalytically active material with low hydrogen overpotential is known for a long time and successfully be used for the situation of numerous organic compound.Platinum, nickel, palladium and rhodium are used for the hydrogenation of methyl phenyl ketone, and palladium is used under the alkene situation, and palladium and nickel are used for the hydrogenation of oil of mirbane.For low cost and the reason that can form king-sized surface (Raney nickel) more simply, nickel surface is very commonly used.Kind electrode successfully is used in the electric catalyticing hydro of unsaturated hydrocarbons such as polynuclear compound, phenol, ketone, nitro-compound, nitrite/ester, imines etc.
In this case, negative electrode uses with different structures.Conducting metal (plate or grid form) for example nickel or V2A steel can cover for example nickel black of same metal porous membrane, can embed the particle of Raney nickel-aluminium alloy or Raney copper-aluminium alloy in described film.Under the situation of using still inactive Raney catalyzer, must activate by suitable pre-treatment.In addition, can use the binding agent of polytetrafluoroethylene (PTFE) as granules of catalyst on the metallic matrix (for example precious metal).
Existing people proposes will be via indigo free radical Direct Electrochemistry indigotin as indirect electrochemical reductive replacement scheme, because described the permanent existence that vat pigment and thioxine dyes do not need the redox medium.This scheme is based on following reaction mechanism: form free radical anion, this free radical of electrochemical reduction then by reaction in the returning between dyestuff and leuco dye.Must at first generate the leuco dye that plays the electronics effect of shuttling back and forth on a small quantity between electrode and dyestuff surface reduces to cause.Use in industrial future for the Direct Electrochemistry reduction of vat pigment, must improve rate of reduction greatly.All experimental datas are that the rate limiting step of this electrochemical process conforms to the reduction of the diffusion control of intermediate free radical anion all.Because this limiting speed key depends on the thickness of electrode surface diffusion layer, can significantly improve rate of reduction so increase the flow of catholyte.But up to now, reactor performance or even bath stability are all still too low.
Electric catalyticing hydro is a kind of method of reducing that is used for vat pigment and thioxine dyes of nearest proposition, and proving bright this method with regard to economic and ecological aspect is a kind of alternative method (referring to for example WO 01/46497) that prospect and magnetism are arranged.This method is made up of a series of reduction steps, and these reduction steps are different on mechanism with aforementioned indirect those steps with the Direct Electrochemistry reduction method via the dyestuff free radical.These reduction steps relate to electronics is transferred to medium or vat pigment from negative electrode leuco compound free radical anion.Different with this mechanism, electrochemical hydrogen turns to following process: adsorbed organic matter matter (being vat pigment) reaction on hydrogen that passes through the generation of water electrolysis original position that adsorbs on the electrode surface and the electrode surface.Step of hydrogenation and evolving hydrogen reaction competition, the efficient of electric catalyticing hydro is by this competition decision.The commercial viability of this variation route is studied in the shunting electrolyzer with the Raney-nickel electrode recently.There are several vat pigments to reduce in this way.For indigo, people have attempted determining that it is 10g/l that top condition in this system and scale have expanded indigo concentration to.Regrettably, adopt top condition, under 95% transformation efficiency, only can obtain 12.7% low current efficiency.Therefore, need huge electrode surface just can make stock solution obtain the feasible rate of reduction of industry above hundreds of square metres.This method only has enough effectiveness to the dye bath stabilization probably.However, still select Raney nickel, because from availability, cost and the stable angle alkaline medium, it is favourable as electrode materials.The poor stability that shows platinum black electrode (wherein the most active electrode) is not so it has industrial applicibility.But on these results' basis, should be by using the efficient that improves this process based on reinforcement dye granule and the interelectrode different reactor design that contacts.For this reason, developed so-called precoated layer electrolyzer (precoat-layer-cell).This reactor is based on work principle of filter, promptly indigoly contacts with negative electrode by making, and wherein said negative electrode is by the carrier (being the strainer fabric) of electro-conductive material and filter the cathodic polarization layer (being Raney nickel) that original position is formed on the described strainer by precoating and form.The critical defect of this technology looks like big pressure drop that forms and the lasting danger of stopping up reactor in filtration procedure.In addition, reactor performance is low.
At the problems referred to above, people have also studied to be carried on noble metal granule on the graphite saccharoid as the electrode materials in fixing and the fluidized-bed reactor.Pressure drop on the granulated material still can have good electrolysis (electrogenolysis) efficient far below the situation of thin Raney nickel powder and its.But precious metal is very expensive and long-term action this catalyzer is poor.
Carbon and graphite are high surface area materials, therefore are widely used in the electrochemistry.Even if for indigo reduction, utilize the negative electrode of special in small, broken bits indigo and Graphite Powder 99, these materials also are applied in the sodium carbonate solution.Recently, found that the graphite saccharoid can be used as the Direct Electrochemistry reductive electrode materials of indigo aqeous suspension.Having sought top condition and scale, to have expanded indigo concentration to be 10g/l (Roessler A, Crettenand D, Dossenbach O, Rys P.JAppl Electrochem, 33:901-908,2003).Because the hydrogen overpotential height on the graphite under application conditions, so very weak hydrogenation absorption cannot or only be arranged.Therefore, normal transfer transport looks like the correlated process of indigo reduction.Regrettably, rate of reduction is quite low.Therefore a large amount of work has concentrated in the acceleration of this process.Till now, can reduce far-ranging vat pigment (being indanthrene dye) and indigo suspension does not stop up reactor up to 100g/l.For example, for indigo research obtained that current efficiency is about 60%, the goodish value of watt consumption 1kWh/kg, rate of reduction 10mg/min kg graphite (under 50 ℃).Therefore, from economic angle, this process can be comparable to the medium technology.The installation cost of this reactor is also lower probably.In addition, need not to reclaim medium by ultrafiltration and nanofiltration.
GB 1239983 discloses a kind of electrochemical method, and wherein grain bed flows through under the effect of fluid electrolyte.These discrete particles conduct electricity, and make electrolyte solution or fluid flow, so that always give particle with mobility.Owing to be positioned at the impervious barrier of particle of grain bed top, so that particle moves upward is limited.Particulate motion is important, because its objective is that the occupied volume of the particle that makes motion is less than the natural volume that occupies as sulfuration bed particle under the non-existent situation of the impervious barrier of particle.This means that flow rate of fluid remains on substantially only is higher than by the definite minimum value of Stokes equations (Stokes equation) to transport particle this barrier that reclines.The low fact of specific conductivity that a problem of this method is a fluidized-bed, this makes this method be not suitable for the reduction of thioxine dyes for example or vat pigment (for example indigo).
US 3966571 has selected a kind of different approach, this patent disclosure a kind of system and method that is used for the two-forty electrochemical reaction, wherein relate to by electrolytical flowing fast and make loose conductive particle be deposited in together electrode.In the disclosure, the conductive particle bed reclines dynamically that sieve is piled up and flows through the chamber fast and keep in touch with sieve formula running contact by ionogen.In order to obtain bed as far as possible closely, to carry out the accumulation of a series of complexity and the circulation of scattering, just after electrolytic process begins, stop.Though this height bed closely makes electrode have high conductivity, must use sizable particle (median size is 1mm) having enough flows, but the high pressure-losses on this unavoidably tight again fixed bed.This causes the electrolytic process that low reaction is surperficial and efficient is quite low and makes the process that is proposed be not suitable for indigo reduction substantially.
Summary of the invention
Therefore, an object of the present invention is not only to provide the improvement of fabric dyeing method discussed above, and totally provide improved electrochemical reactor, described improved electrochemical reactor to have high-level efficiency, high-throughput, be easy to safeguard and can easily incorporate in existing oxidation or the reducing process device.
Therefore, proposed a kind of electrochemical reactor, described electrochemical reactor comprises that at least one has wherein encapsulated the liquid chamber of a large amount of conduction saccharoids that freely suspend.At least one sidewall of described chamber is an electrode, and relative sidewall is formed by dividing element (that is, for example film and/or grid).Bottom inlet and top exit are provided for catholyte or anolyte on the described chamber, so that in fact liquid flow to the top with upward movement from the bottom.The inlet region of described chamber and outlet area provide grid and Under The Grille, and its mesh width and location are chosen as and make catholyte or anolyte flow to the top from the bottom but stop saccharoid to leave described chamber by grid.The definition that it should be noted that the above-mentioned saccharoid that freely suspends refers to that the motion of the mobile saccharoid of short of liquid just is not subjected to the restriction of described two grids.Therefore, the structure that is proposed is not the so-called fixed bed of conductive particle fixed in the space wherein, but towing bed (a dragged bed).The upwelling that this means catholyte or anolyte is adjustable as and makes the described a large amount of saccharoid antagonistic action that is in operation be transported to recline in the gravity of saccharoid and go up grid, and (when flowing by force when being enough to be dragged to particle or saccharoid on the grid fully) Under The Grille does not contact with saccharoid substantially in this case.
Therefore, with wherein the tightly packed fixed-bed reactor between two grids of particle are different, in the device that is proposed, deliberately make loose particles ground between two grids, so that in service they pulled or pushed to recline and gone up grid, and they will not move downward on the Under The Grille under gravity when having liquid-flow.The reactor that is proposed is also different with so-called fluidized-bed reactor; in so-called fluidized-bed reactor, exist liquid to flow to the grain bed at top from the bottom by it; but wherein do not go up grid and wherein liquid flow always be adjusted to make liquid effect of dragging much smaller than the particulate action of gravity, so that particle substantially always drops on the Under The Grille.
Therefore; a key feature of the present invention is the following fact; promptly, particle or saccharoid go up grid because being reclined by towing; so but the electroneutral bed of going up grid and high porosity being provided that reclines is piled up on their optimum ground, therefore present liquid flow through they the time little, the high-efficiency electrochemical of pressure drop react optimum high surface area and owing to intergranular contact and the desirable combination that rubs and contact at each intergranular optimum height.Optimum ground, be deposited in and be not meant on the meaning of the present invention that the particle rearrangement is to arrange the most closely, and be meant that particle packing is stable and the closely relative arrangement of contact, thereby obtain required high conductivity, high reaction surface on the one hand, obtain high porosity on the other hand to realize ionogen high throughput and high reaction rate.If ionogen has quite high viscosity, high porosity is particularly important also, and this may be the problem of a sternness under for example dyestuff such as indigo vatting situation.
In first preferred embodiment of the present invention, the median size of saccharoid is less than or equal to 0.5mm, preferably between 0.2-0.5mm, even more preferably median size in the 300-400 micrometer range, but preferably all particulate diameters all greater than 5 microns.In fact, if saccharoid selects too smallly, the particle of grid has the tendency of total blockage liquid-flow by reactor on then being reclined by towing usually, and is too much if saccharoid selects, grid or electrochemical efficiency were low excessively on then they can not be reclined by towing, so advantageous effects can not realize.
According to another preferred embodiment of the present invention, the distribution of sizes of saccharoid makes that (full width at half height fwfh) in the 50-100 micrometer range, does not wherein preferably exist and is less than or equal to 5 microns saccharoid full width at half maximum.Preferred saccharoid is that non-sphere is so that described towing bed accessory has high porosity substantially.In order to hold back the saccharoid of this size, advantageously make at least one, the mesh width of preferred two grids is less than or equal to 200 microns, preferred mesh width is in the 50-150 micrometer range.Grid can be polyester perforate fabric or other plastic materials.
In order to realize effective electrochemical reaction, preferred described saccharoid is gac, coke and/or graphite saccharoid, and it is optional through surface treatment (for example improving the chemical reactivity on specific conductivity or surface).Also can use different common electrode materials to resemble the saccharoid of metallic particles and conductive polymers.
In order to ensure described saccharoid is freely to suspend really, the cumulative volume during the basic dense accumulation of a large amount of saccharoids that the volumetric ratio between preferred two grids is lived by the encapsulation of two grids greatly at least 10%, and preferably greatly at least 25%, even more preferably greatly at least 40%.
If electrode wall and dividing element, if very typically the distance between the membranous wall of described chamber is in the 0.5-5cm scope, preferably in the 0.5-1.5cm scope and/or the height of described chamber in the 10-60cm scope, then can set up top condition.
As already mentioned, in described device, common two grids all are electroneutral, so it does not form the part of electrode.
A special preferred embodiment is that described chamber is a cathode compartment, and one of them sidewall is that negative plate and relative sidewall are the dividing element (being film, grid) of described cathode compartment and adjacent anode chamber.
Preferred described electrochemical reactor is piled up by the level of above-mentioned reactor and obtains.Therefore, described electrochemical reactor preferably includes at least two adjacent one another are of preferably having alternating polarity, preferred electrolyzer unit as defined above more than two, is that adjacent unit forms the common battery lead plate so that comprise the adjacent wall of the adjacent cells of cathode compartment and anolyte compartment.
In addition, the present invention relates to use the method for this class reactor oxidation or reduction chemical composition, these class methods not only are used in the pure chemical field and also are used in the biological technical field.In reactor, reduce or the method for oxidation component is characterised in that the catholyte that carries described component or the lift velocity of anolyte are chosen as the minimum fluid velocity (υ that determines greater than by following equation with continuous or semi-continuous process
m):
υ
m＝[(ρ
s-ρ
f)gd
p 2]/μ，
Wherein, υ
m=minimum flow velocity, ρ
sThe density of=saccharoid, ρ
f=fluidic density, g=universal gravity constant, d
p=median size, μ=fluid viscosity.If in operational process, keep these conditions, can guarantee that particle or saccharoid are pulled the upward grid that reclines really securely.
The advantageous applications of this method is that described component is vat pigment and/or thioxine dyes, bleaching component or the reduction medium in the aqueous solution.
As indicated above, according to the present invention, need that piling up securely reclines and go up grid but be not towing bed fully closely.For fear of the described towing bed of compacting in operational process or before the operation, according to another embodiment of the present invention, with fluid velocity υ
mBe adjusted to and make to have laminar flow at least in passage area before fluid enters the towing bed, wherein preferably this is following acquisition by selecting fluid velocity:
υ
m<500μP/S＊(ρ
f)[10(1-ε)/ε
3]，
Because required laminar velocity υ in the bed exterior passage way
McProvide by following formula:
υ
mc<500μP/S＊(ρf)
And υ
mAnd υ
McHave following relation:
υ
m＝υ
mc[10(1-ε)/ε
3]。
The invention still further relates to the method for the towing bed of the method operation that preparation gives according to top subsequently.This method is guaranteed basically that described particle is reclined by towing in the mode of avoiding the described bed of compacting basically and is gone up grid.According to this method, in the first step, electrolytical fluid velocity increased to up to or be higher than minimum flow velocity according to Stokes equations, but preferably be no more than the twice of the minimum value of Stokes equations, and remain to the conduction saccharoid that freely suspends at least and reclined by towing and go up grid.In second step, flow velocity increased to the minimum value in following scope then:
υ
m＝[(ρ
s-ρ
f)gd
p 2]/μ，
Preferred paramount but do not comprise following value:
υ
m<500μP/S＊(ρ
f)[10(1-ε)/ε
3]。
For this reason, the flow velocity in the preferred towing passage upstream is υ
McIncrease with per second 0.001～0.05cm/s, preferred per second 0.005～0.02cm/s.Actual electrolytic process begins (preferably should not allow electric current to flow before this) in the 3rd step, wherein preferably keeps the variation of flow velocity little of to avoid the towing bed to reset and compacting towing bed then.
In addition, the present invention relates to the purposes of reactor as mentioned above, preferably with the top given fiber that is used for, the method coupling of the urn of yarn and/or fabric and/or sulfur dyeing, wherein said reactor be used for preparing SYNTHETIC OPTICAL WHITNER and/or be used for vat dyes and/or under the help of medium system, be used for stablizing the anti-oxidation of dye bath and/or with dye application to fiber, be used for the described dyestuff of oxidation after on yarn and/or the fabric, wherein preferably use two independently reactors, one is used for preparing SYNTHETIC OPTICAL WHITNER and with the described dyestuff of oxidation after dye application is to the fiber, and another is used for reducing described dyestuff.
Other embodiments of the present invention provide in subsidiary claims.
Therefore, in short, the present invention relates to be used for the novel electrode structure of electrochemical reactor: the towing bed electrode, described towing bed electrode is made of conduction granulated material and conducting plates.Granulated material constitutes by the high porosity bed of electrolyte flow so that flowing of antigravity pulled.Described bed is remained in the reactor and with conducting plates by nonconducting net and contacts, and described conducting plates is passed to granulated material with electric current.This electrode has high-specific surface area, high reduction rate and has high porosity, can avoid reactor plugs.It is particularly suitable for reducing the suspensoid or the gas (as oxygen) of organic compound (as vat pigment and thioxine dyes), because this form can make compound to reduce with the mode that electrode closely contacts and the pressure drop of reactor is minimized.Also proposed a kind of dyeing installation among the present invention, described equipment can be equipped with the only bleaching of realization cellulosic fibre on a dyeing machinery of electrochemical reactor of carbon granule towing bed by use, the reoxidizing described dyeing keratin-fiber and material with vat pigment or thioxine dyes.Described reactor forms hydrogen peroxide and treats painted matrix, reduction vat pigment or thioxine dyes, is present in lower concentration that medium in the reactor stablize dye bath and at formation oxidation dye behind the bath exhaustion with dyestuff fixing necessary hydrogen peroxide on described matrix by reduction with bleaching in alkaline medium.
The purposes of the electrode that is made of granulated material is known equally.Electrochemical reactor with fixed bed or fluidized-bed can be found in the literature.But the towing bed that is proposed is a new invention and has beat all efficient.The present invention can use by minor diameter (the electrode work that＜0.5mm) saccharoid constitutes.This is impossible in fixed bed, because for the saccharoid of this size, the pressure drop of reactor is too high, this has limited the specific surface area and the performance thereof of electrode.Fluidized-bed causes the loss of a specific conductivity, and this also will limit its performance, and in addition, the droop loss in the fluidized-bed is far above the towing bed.
The accompanying drawing summary
The preferred embodiments of the invention have been shown in the accompanying drawing, wherein:
Fig. 1 is the detailed sectional view of electrochemical reactor elementary cell a); 1b) be piling up of five these class elementary cells;
Fig. 2 shows the comparison of the pressure drop that takes place in the different system;
Fig. 3 shows the possible path of biotechnology applications;
Fig. 4 illustrates the standard coloring process according to prior art;
Fig. 5 shows has two synoptic diagram according to the coloring apparatus of reactor of the present invention; With
The compare and measure figure of Fig. 6,7 for comparing with art methods.
Detailed description of the preferred embodiments
Below with reference to accompanying drawings the electrochemical cell with towing bed electrode is described in detail, wherein the purpose of accompanying drawing is unrestricted the preferred embodiments of the invention for the preferred embodiments of the invention are described.
The present invention relates to a kind of electrochemical reactor, described reactor comprises the porous electrode of at least one conduction granulated material shape.For obtaining existing in the literature the mentioning of cardinal principle that high-specific surface area uses the electrode that is made of granulated material.Utilize the reactor of this principle can be divided into two kinds of different types: fixed bed electrode and fluid-bed electrode.
But up to today, none can use diameter to come work and do not cause big pressure drop that can not put up with or the reduction that does not cause specific conductivity in the bed and corresponding suboxide or reduction efficiency in the process that ionogen passes through less than the particle of 0.5mm in these reactors.This has limited the performance of reactor, because its effectiveness depends on the specific surface area of electrode, and the specific surface area of electrode reduces along with the particulate size that forms electrode and increases.
The present invention proposes a kind of new texture that constitutes the bed of electrode because this electrode by with the rightabout electrolyte flow towing of gravity and by nonconducting grid " lock " in reactor, so the mesh of grid is less than particulate size in the bed.This structure can obtain the fixed bed or the bed porosity of the fluidisation height of bed and the less pressure drop that constitute than the particle by same size.In order to obtain to pull bed electrode, many geometrical shapies of reactor all can be considered.
The grid structure of plate-and-frame filter press is the simplest for this application.The handiness of this reactor highly significant because be highly susceptible to making up the reactor of staple (staple) with many electrodes or heap form and also can select the desired thickness of electrode vessel.The general direction of electrolyte flow is vertical with electric current.This structure can make the electrolyzer rearrangement and realize the volumetrical optimum utilization.In addition, the simple geometric shape of reactor has limited when the size of reactor and has increased the problem that occurs with before the process industryization or during industrialization reactor (enlarging in proportion).Last but considerablely be to be highly susceptible to according to the material that should be used for changing electrode.
Fig. 1 a) shows the feasible configurations of pressure filter reactor.Electrochemical reactor 1 comprises anolyte compartment 2 and adjacent cathode compartment 3.Provide film 6 between two chambers, film 6 is generally the Nafion film.Anolyte compartment 2 and film 6 relative walls are provided by positive plate 4, and the wall that cathode compartment is relative with film is provided by negative plate 5.Correspondingly, electric current is as shown in arrow 12 flows.
In cathode compartment 3, provide a large amount of particulate form the bed, but these saccharoids do not fill up fully two grids 11 ', 11 " between the space.The Flow-rate adjustment that the situation of Fig. 1 shown in a) shown liquid for make saccharoid by towing recline go up grid 11 ' and at Under The Grille 11 " with the situation of the freeboard of the no saccharoid of existence between the nethermost saccharoid.
If such reactor is used for reducing vat pigment, then dyestuff will enter via inlet 9, and described dyestuff will leave reactor and be ready to be applied to fabric to go back ortho states via outlet 10.In corresponding process, in anolyte compartment 2, will produce oxygen.
As Fig. 1 b) as shown in, have alternating polarity if the unit that provides in a) as Fig. 1 is adjacent one another are and arrange that then they can pile up with the effective means level.They can be as Fig. 1 b then) in the entrance and exit path shown in connect effectively.
Illustrating among Fig. 2 as carbon granule height of bed 10cm and when the pressure drop during by described bed of 50 ℃ 1M NaOH ionogen.Obviously, for identical particle size, the pressure drop in the towing bed (17,18, the particle size of corresponding 0.32-1.16mm of difference and 0.50-0.40mm) is significantly less than fixed bed (16,1.41-1.00mm particle size) or fluidized-bed (15, the particle size of 0.32-0.16mm) in pressure drop.Pressure drop is significantly less to be because the porosity height of towing bed.In this system, described bed can not self reorganization so that its particle close mode in an ideal way.The tightness of towing bed is little, because the formation of this bed has increased the incidence of vault (vault) and empty bag (empty pocket).
Defective in the close body (compactness) keeps in position with certain class vault, and described vault is the result who assembles balance (collective equilibrium), wherein relates to a large amount of particles.Because particulate surface folding and shape are so intergranular friction is very important.It is opposite that the friction participant makes particle occupy rotatablely moving of higher position.These vaults that form in the forming process of bed are to be difficult to destructive.Therefore, the pressure that is applied on the vault by the liquid of the bed of flowing through will be by improving the stability of vault more around the particle extruding that constitutes described vault.This pressure is invalid to improving tightness, but can improve the specific conductivity of bed.In fact, improve with the pressure that the liquid of the contact that may have quality bad luck between the relevant particle of insulation layer around the fold on surface and the particle by the bed of flowing through is applied on the bed.Two kinds of effects all help electrochemical process.In addition, if having one deck solid particulate coacervate to be restored or insoluble impurity to rest on the inlet of bed or finally rest on the centre of bed, the system that then has towing bed is better.In fact, flow reduce bed is disintegrated and discharge solid particulate.
In some cases, also can obtain liquid from overhead stream to the bottom, have enough tightness defectives the bed.But bed is disintegrated and discharge solid particulate.
Described reactor is an ideal for the reduction of suspensoid.The bigger serface that porous electrode is given allows the process of little exchanging electrical current to have a great attraction for every surface unit.In addition, this form can increase mass transfer coefficient, plays the effect of turbulence promoter because it is the flow through ionogen of bed.Contacting between suspended particle and granulated material is best, and it is moderate that the pressure drop of reactor keeps.For the reduction of vat pigment and thioxine dyes, aerated (carbonated) granulated material is allowed to obtain good reactor per unit volumetric productivity as electrode.This process also can be used for the restoring operation in the dyeing course.
Described towing bed electrode structure is that a kind of gas phase, liquid phase (ionogen) and solid phase (electrode) of making contacts to realize the favorable structure of electrochemical conversion.For example, confirmed that oxygen can be converted into H with electrochemical means on the material identical materials of painted vat pigment and thioxine dyes with being used for reducing
2O
2
It is meaningful especially to learn the mode that transforms multiphase mixture with high performance electrochemical, because can avoid some sepn processes.The present invention allows the electrochemical conversion in homogeneous phase ionogen, suspensoid, emulsion, the foam etc.The present invention can obtain the many application reduction or the oxidation of mineral compound (organic and) in chemical industry, also can be applied in biotechnological industries, for example according to the regeneration of scheme shown in Fig. 3 cofactor.
The present invention allows to propose a kind of new coloring system that can be used for using the coloring process of vat pigment (comprising indigo) and thioxine dyes.Use this class dyestuff based on the dyestuff of reduction at present with the acquisition water-soluble form.Under the reduction form of dyestuff, described dyestuff has direct colourability to cellulosic fibre, and reduce after on absorbing fiber the dyestuff of form will be in fiber original position reoxidize and be original water-insoluble form.
The coloring process of standard is by the block representation among Fig. 4.Treat that painted material prepares (3.2.1) by boiling and carrying out oxide treatment with superoxide in the presence of alkali.
Water-insoluble dyestuff must be converted into water miscible substantive dyestuff form before the dying operation.This is by reaching (3.2.3-3.2.2) with the reductive agent reduction.In the modern fabrics dyeing, the reduction of vat pigment is carried out with strong reductant.That the most frequently used is V-Brite B (Na
2S
2O
4).Regrettably, the disposal of dye bath and rinse water causes problem, and this summarizes in the above.In addition, owing to need to use a large amount of excessive reductive agents to stablize the dye bath of easy oxidation, so may contain excessive hyposulfite in the waste water.In fact, for avoiding the defective in painted, dyestuff must always be in the reduction form.
Cellulosic fabric enters dye bath then, and the dyestuff in the dye bath is entered (3.2.4) in the fiber by exhaustion.When exhaustion technology was finished, the rinsing DYED FABRICS was to remove unstable dyestuff and remaining reductive agent (3.2.5).The dyestuff of water-soluble form changes its original form into again by oxidation.At present, this carries out (3.2.6) with hydrogen peroxide usually.
After the oxidation, DYED FABRICS is handled (soaping), rinsing and dry under the boiling condition in the aqueous solution of tensio-active agent.
The system that is proposed can produce pre-treatment and treat to reoxidize the required hydrogen peroxide of dyestuff (3.2.6), can prepare the dye bath (3.2.2 adds 3.2.3) of no reduction measure and can stablize this bath after coloring material (3.2.1) and the exhaustion.This system can adapt to the different dyeing machinery that exists on the market.
Scheme shown in Fig. 5 is the design of cheese dyeing machine.Standard dyeing machinery in the industry often is equipped with and is used for preparing the jar of dye bath and chemical is added in permission at coloring process less jar.
Can on this standard set-up, increase by two electrochemistry pressure filter reactors 25 and 26 with carbon granule (or graphite granule) towing bed negative electrode.The activity of this electrode materials is relevant with the functional group that the oxidation that exists is gone up on its surface.Particularly relevant with the quinhydrones group with quinone, no matter be directly connected on the carbon surface or be the part of more complicated structure.On this electrode, can produce H by oxygen
2O
2, reduction vat pigment or thioxine dyes and reduction contain other organic compound of quinonyl.By the electrochemical reactor that is equipped with carbon granule towing bed negative electrode, we use this electrode to carry out the different operating of dyeing course especially.
Yarn bobbin is placed dyeing machinery 20, and the alkaline solution that will prepare in urn 23 is then introduced in the machine 20.This solution moves through reactor 25 and constitutes catholyte.Anolyte provides via jar 27, is the NaOH of 1M.Oxygen or air are introduced the bottom of reactor 25, but make the required superoxide original position of bleached fiber form.When pre-treatment is finished, empty liquid lime chloride and also will contain in the new alkaline solution introducing dyeing machinery of a small amount of medium.
This compound (it can be the anthraquinone of solubility) is used for eliminating the oxygen that exists in the dye bath and stablizes dye bath in dyeing course.Alkaline solution moves through electrochemical reactor 25, and medium is reduced.Selected medium should have the redox-potential more negative than the reduction potential of dyestuff.Therefore, in the presence of the reduction medium, dyestuff will be in its reduction form fully.Medium also can be eliminated dissolved oxygen in the solution.Dye bath can remain under the rare gas element (for example as jar 21 nitrogen that provided) to remove oxygen and to reduce electric consumption.
In second electrochemical reactor 26, reduce and produce strong solution as the dye suspension (for example suspensoid in 1M NaOH of 100g/l) that provides in the jar 28 through the reductive dyestuff.Then this solution is introduced in the dyeing machinery.In this case, anolyte provides via jar 29, still is the NaOH of 1M.Can measure and be in its dyestuff of going back ortho states in the painted bath and make and to obtain better tinctorial quality.From described machine, empty the dye bath of exhaustion.The rinsing yarn bobbin, and then by oxygen reduction in first electrochemical reactor 25 produce hydrogen peroxide so that dyestuff oxidation and fixation on fiber.
The process that is proposed makes consumption of raw materials reduce and limit the cost of wastewater treatment in a large number.
For obtaining the towing bed, should select the minimum fluid velocity of determining by following equation:
υ
m＝[(ρ
s-ρ
f)gd
p 2]/μ，
Wherein, υ
m=minimum flow velocity, ρ
sThe density of=saccharoid, ρ
f=fluidic density, g=universal gravity constant, d
p=particle diameter, μ=fluid viscosity.The flow velocity of selecting can guarantee to act on gravitational effect on the particle less than the towing force that is applied to top mobile fluid from the bottom more than or equal to as above determined value in reactor.
It should be noted that top minimum flow velocity value υ
mFlow velocity in yes the towing bed, its minimum value are actually 10 times of the minimum velocity that calculated when the use Stokes equations.This minimum velocity can realize pulling the complete stabilityization of bed structure.
This minimum flow velocity can with empty passage in (or enter towing bed before) can easier measurement/control fluidic speed υ
McRelated.υ
McCan be expressed as minimum flow velocity υ in the towing bed
mFunction:
υ
mc＝[ε
3/{10(1-ε)}]＊υ
m
Wherein, ε is the porosity of towing bed, and the value of ε for example is worth in the 0.6 expression bed 60% volume and is occupied by fluid in the 0-1 scope, and 40% is occupied by particle.
Advantageously, this has been avoided the particle in the towing bed to reset in operational process substantially.For guaranteeing basic not rearrangement in the operational process of towing bed, the fluidic top speed should be adjusted to make in the empty passage laminar flow in the passage.For this reason, speed υ
McShould be lower than the velocity amplitude when beginning to become non-laminar flow when flowing, so
υ
mc<500μP/S＊(ρ
f)
Wherein, P is the girth of passage, and unit is a rice; S is the cross section of passage, and unit is square metre that μ is the same, is fluid viscosity.
Therefore, (or before towing bed) flow rate of fluid υ in the preferred empty passage
McWithin the Ying Zairu lower boundary:
[ε
3/{10(1-ε)}]＊[(ρ
s-ρ
f)gd
p 2]/μ≤υ
mc<500μP/S＊(ρ
f)
This means that again the flow velocity in the towing bed should be within as lower boundary:
[(ρ
s-ρ
f)gd
p 2]/μ≤υ
m<500μP/S＊(ρ
f)[10(1-ε)/ε
3]。
For channel cross-section is 0.10 x 0.01m, carbon granule density p
sBe 2.30g/cm
3, average diameter of particles d
pBe 0.450*10
-3M, fluid (1M NaOH, 50 ℃) density p
fBe 1.03g/m
3, viscosity, mu is 1.24*10
-3The carbon granule towing bed of Pa.s, the minimum flow velocity value that obtains is 4cm/s, and higher limit does not reach 14cm/s to avoid non-laminar flow.
It should be noted that according to Stokes equations, at the flow velocity υ of 0.4cm/s
mPromptly formed down by towing recline the towing bed of going up grid (fluidized-bed in addition lower flow velocity for example promptly formed under the 0.2cm/s, but be not enough to all particles are pulled the upward grid that reclines fully), but under this flow velocity, with regard to operation of the present invention, specific conductivity, stability and the reaction efficiency of bed are low excessively.
For the actual formation of towing bed according to the present invention, can follow following program:
At first make electrolytical flow velocity between 0.4 to 1cm/s, between preferred 0.4 to 0.6cm/s.This causes the not closely formation of the bed of grid but the quilt towing reclines.In fact, when starting like this, bed is upwards delivered the grid that reclines by electrolytic liquid immediately, even also like this before bed is passed through fully by liquid.Bed is held back by grid and is fixing then.The liquid bed of will flowing through fully then.
Subsequently flow velocity is slowly increased to according to value of the present invention.Slowly the common flow velocity of expression increases the υ in reaching above-mentioned scope with per second 0.001-0.05cm/s, preferred per second 0.005-0.02cm/s
McValue, i.e. 4cm/s but be lower than 14cm/s at least is preferably between 4cm/s and 8cm/s.
Begin actual electrolytic process subsequently, carefully make the variation of flow velocity keep little undesirable towing bed close mode that causes to avoid the towing bed to reset.
With regard to particle, its size should be in the 1-1000 micrometer range, between the preferred 50-500 micron.In addition, in order to make the towing bed accessory high porosity being arranged, will be favourable when particle is not full spherical.Usually, the particulate sphericity should be in the 0.6-0.8 scope.In fact, almost be spheric as fruit granule, then they may " automatically " rearrangement be dense packing sometimes, thereby cause the low porosity in the 0.36-0.42 scope usually.Use the particle of above-mentioned sphericity, can reach extremely high even be higher than 0.6 porosity (mean that 60% volume is occupied by liquid in the towing bed, 40% volume is occupied by particle).Therefore, it is preferred having the quite aspheric particle of uneven surface and overall shape, because they will produce the more towing bed of high porosity under these conditions.This class particle promotes the formation of cavity, is the formation of the sizable cavity of size sometimes, and this is because particulate is stablized collective's positioned opposite, can relate to many particles in this layout.If spheroidal particle, then such layout is not easy to generate so.
Embodiment
What embodiment 1 described is the structure and the indigo reduction in this reactor of electrochemical reactor.
Reactor (Electro MP-cell, Electrocell AB, Sweden) is formed by being pressed in the spacer between the two end plates and the combination of liner.The towing bed that uses smooth nickel plate (10 x 10cm) and graphite saccharoid (50g) is as working electrode.The particle diameter of graphite granule is between 0.7 to 0.05mm, between preferred 0.5 to 0.2mm.Anode is nickel plate (10 x 10cm).(Nafion324 DuPont) separates two chambers to use commercially available Nafion film.
In 3 liters jar, be dispersed in 2 premium on currency 20g is indigo, also contain 80g purity in the water and be 100% caustic soda pellet.This catholyte solution is remained under the nitrogen atmosphere and cathode compartment is passed through in pumping.In another jar of 3 liters, put into 2 liters of water that contain 80g caustic soda.This anodolyte solution is pumped through the anolyte compartment.To top vertically flow through cathode compartment and anolyte compartment, flow velocity is 1l/min from the bottom for catholyte solution and anodolyte solution.
By apply-cathode potential (with respect to the Ag/AgCl in the 3M KCl solution) of 1000mV makes the dye suspension reduction.Catholyte solution and anodolyte solution remain under 50 ℃.These reductive conditions are used 7h, the indigo leuco dye that is reduced to fully, current efficiency is about 95%.
Reactor is formed (ElectroProd-cell, Electro-cell AB, Sweden) by 12 reactive tanks that connect together in the pressure filter mode.With identical among the embodiment 1, each reactive tank is the combination of spacer and liner.Negative electrode is by a nickel plate (surface-area 3600cm
2) and the towing bed of a graphite saccharoid (4000g) form.Anode is nickel plate (60 x 60cm).(Nafion 324, DuPont) separate two chambers to use commercially available Nafion film.
In 200 liters jar, 20kg vat pigment or thioxine dyes are dispersed in 160 premium on currency, also contain 80kg purity in the water and be 100% caustic soda pellet, be 50 liters of water that contain 2kg caustic soda in another jar of 60 liters.Make the pH of this anodolyte solution remain on 14 by adding caustic soda.To top vertically flow through cathode compartment and anolyte compartment, flow velocity is 150l/min from the bottom for catholyte solution and anodolyte solution.
By apply-cathode potential (with respect to the Ag/AgCl in the 3M KCl solution) of 1000mV makes the dye suspension reduction.Catholyte solution and anodolyte solution remain under 50 ℃.Keep these reductive conditions and be reduced to leuco dye fully until dyestuff.
Can under nitrogen atmosphere, introduce leuco dye in the special container and be sent to the dyehouse.Available then volume pump is introduced this dope in the dye bath.This system is suitable for discontinuous or the successive dyeing apparatus.
Reactor among electrochemical reactor and the embodiment 2 is similar.The first step is with mode indigotin at intermittence similar to Example 3.Then, when obtaining the indigo leuco compound solution of 100g/l in the catholyte tank, introduce the indigo suspensoid of 100g/l by volume pump in this jar, flow is 2l/min.The indigo suspensoid of introducing contains the caustic soda of 40g/l, so have and the identical composition of reduction step at intermittence.In parallel mode the indigo leuco compound solution of the 100g/l flow velocity with 2l/min is metered to the storage tank from catholyte tank.Storage tank is used for supplying with successive rope dyeing machine.
Electrochemical reactor described in the embodiment 1 is connected in the dye bath of laboratory.What be used for the reductive dye bath consists of 4g/l NaOH, 0.5g/l 9,10-anthraquinone-2-sulfonic acid-Na salt and 1g/l C.I. SULPHUR BLACK 1 200.During beginning, apply-cathode potential (with respect to the Ag/AgCl in the 3M KCl solution) of 1000mV and 50 ℃ temperature reduction dye bath.The redox-potential of bathing is risen to-500mV, and dyestuff is reduced fully.On the reductive dyestuff, dying in the process, making electromotive force value of being maintained fixed of dye bath by the control flume electric current.
Reactor among electrochemical reactor and the embodiment 1 is similar.The NaOH that uses 2 liters of 1M is as catholyte and the O of not cut-off under atmospheric pressure
2Put into the NaOH of 2 liters of 1M in the anode electrolyte tank.To top vertically flow through cathode compartment and anolyte compartment, flow velocity is 1l/min from the bottom for catholyte and anolyte.
Apply the working current of 5A, obtain 2% H behind the 12h
2O
2Solution.This solution can be used to bleached paper in Pulp industry.Therefore, in textile industry, can be used to bleached cellulose fibres or reoxidize leuco dye with the industrial peroxide solutions of the reactor production that provides in embodiment 1 or 2.
Embodiment 6 has described the application of the present invention in biotechnological industries: by the electrochemical reduction regeneration enzyme cofactor NADH of NAD+.Purpose is to produce D-N.F,USP MANNITOL by D-fructose enzymatic.Mannitol dehydrogenase (its enzyme for using in the production of D-N.F,USP MANNITOL) is that NADH is dependent.
Identical reactor in the use and 1.0.5mM NAD+, 100mM D-fructose, 1000U/l mannitol dehydrogenase and 100mM sodium formiate/phosphate buffered saline buffer (pH7.0) are put into catholyte tank.The phosphate buffered saline buffer (pH7.0) of 0.5M is put into anode can.Apply-cathode potential (with respect to the Ag/AgCl in the 3M KCl solution) of 1200mV, dye suspension obtains electrochemical reductions down at 25 ℃.These conditions are kept 50h so that D-fructose is converted into D-N.F,USP MANNITOL fully.
Quantitative and qualitative comparison with art methods
Below disclosed two kinds of processes among identity basis reactor/method of the present invention and GB 1239983 (below be called D1) and the US 3966571 (below be called D2) there are in essence different.
For this reason, will the condition according to D1 and D2 be compared with condition according to the present invention.
Fig. 6 shows the pressure-losses with the comparison diagram form, and (millibar/cm) (y-axle) as rate of flow of fluid (cm/s) (x-axle, υ
Mc) function.The condition of giving at be that mean sizes is the particle (among Fig. 7 too) of 0.4-0.5mm.As can be seen, under the fluidized-bed situation according to D1, flow velocity can not increase to the value that is higher than about 0.7cm/s, because when being higher than this value, reactor will be no longer consistent with D1, and particle will be no longer mobile.It can also be seen that under the fixed bed situation according to D2, because particulate imporosity in this bed, under the flow velocity of 1cm/s, the pressure-losses just increases to the value of 350 millibars/cm very apace low.
This shows for the required high flow rate of high-efficiency electrochemical reaction, and these two do not have which to suit in open.
It can also be seen that because the porosity height, so towing bed according to the present invention can make flow velocity increase to high value to 6cm/s, and the pressure-losses in the towing bed still lower (always be lower than 100 millibars/cm).Fluid electrolyte flow through the bed this high flow rate realized according to unexpectedly high speed of reaction of the present invention.
In another experiment, in Fig. 7, compared the specific conductivity of different beds.Provided the function of specific conductivity (1/ (ohm .cm)) (y-axle) in this case as flow velocity (cm/s) (x-axle).As can be seen, have inherently according to the fluidized-bed of D1 and be lower than 25 low-down specific conductivity.In principle, the fixed bed according to D2 has high conductivity under the flow velocity of 0.8-1.2cm/s.But the speed of reaction under these low flow velocitys is just simply too low for great majority are used.
Different with as can be seen from Figure 7, for the entire area until the flow velocity of 6cm/s, towing bed according to the present invention can have and is higher than 200 high conductivity.
Reference numerals list
1 electrochemical cell, electrochemical reactor
2 anode chambers
3 cathode chambers
4 positive plates
5 minus plates
6 films
7 anolyte entrances
The outlet of 8 anolytes
9 catholytes inlet
The outlet of 10 catholytes
11 grids
12 senses of current
13 have the reactor stack of the electrode that is stacked
14 saccharoids
15 fluidized-beds, 0.32-0.16mm
16 fixed beds, 1.41-1.00mm
17 towing beds, 0.32-0.16mm
18 towing beds, 0.50-0.40mm
19 fixed beds, 4.00-2.00mm
20 dyeing pots
21 protective atmosphere containers
22 additive tank
23 alkaline solutions/medium jar
24 oxygen containers
25 first electrochemical reactors
26 second electrochemical reactors
The anolyte tank of 27 first reactors
The catholyte of 28 second reactors and tinting material suspensoid jar
The anolyte tank of 29 second reactors
The P valve
Claims (18)
1. electrochemical reactor (1,13), described electrochemical reactor comprises that at least one has wherein encapsulated the liquid chamber (3) of a large amount of conduction saccharoids (14) that freely suspend, at least one sidewall (5) of wherein said chamber is an electrode, relative sidewall is formed by dividing element (6), wherein on described chamber, provide bottom inlet (7 for catholyte (9) or anolyte (7), 9) and top exit (8,10), the inlet region of wherein said chamber (3) and outlet area provide grid (11 ') and Under The Grille (11 "); its mesh width and location be chosen as make described catholyte (9) or described anolyte (7) flow to the top from the bottom but stop described saccharoid (14) by grid (11 '; 11 ") and leave described chamber (3), and the upwelling of wherein said catholyte (9) or described anolyte (7) be adjustable as described a large amount of saccharoids in service (14) pulls recline described on grid (11 ') and described Under The Grille (11 ") do not contact with described saccharoid (14) substantially.
2. according to the reactor (1 of claim 1,13), the median size of wherein said saccharoid (14) is in the 1-1000 micrometer range, be preferably greater than 50 microns and be less than or equal to 0.5mm, more preferably between 0.2-0.5mm, in addition more preferably on average non-but generally particle diameter in the 200-500 micrometer range.
3. according to each reactor (1,13) in the aforementioned claim, wherein preferably there is not the saccharoid (14) that is less than or equal to 5 or 50 microns in the size distribution full width at half maximum of wherein said saccharoid (14) in the 50-100 micrometer range.
4. according to each reactor (1,13) in the aforementioned claim, wherein at least one, preferred two grids (11 ', the mesh width of 11 ") is less than or equal to 200 microns, preferred mesh width is in the 50-150 micrometer range.
5. according to each reactor (1,13) in the aforementioned claim, wherein said saccharoid (14) is the particle and/or the graphite saccharoid of gac, coke, metallic particles, conductive polymers, and it is optional through surface treatment.
6. according to each reactor (1 in the aforementioned claim, 13), wherein said two grids (11 ', 11 " volumetric ratio) by described two grids (11 '; the cumulative volume during described a large amount of saccharoids (14) dense packing of 11 ") encapsulation greatly at least 10%, preferably greatly at least 25%, even more preferably greatly at least 40%.
7. according to each reactor (1 in the aforementioned claim, 13), wherein said dividing element (6) is film (6) or grid, and the described electrode wall (5) of described chamber (3) and the distance between described membranous wall (6) are in the 0.5-5cm scope, preferably in the 0.5-1.5cm scope.
8. according to each reactor (1,13) in the aforementioned claim, the height of wherein said chamber is in the 10-100cm scope.
9. according to each reactor (1,13) in the aforementioned claim, wherein said two grids (11 ', 11 ") all are electroneutral.
10. according to each reactor (1 in the aforementioned claim, 13), wherein said chamber (3) are cathode compartment, and one of them sidewall is negative plate (5), relative sidewall is the dividing element (6) of described cathode compartment (3) and adjacent anode chamber (2), and described dividing element is preferably film.
11. electrochemical reactor (1,13), described electrochemical reactor comprise at least two, preferred more than two according to the reactor of claim 10, it is disposed adjacent one another and have alternating polarity, is that adjacent unit forms the common battery lead plate so that comprise the adjacent wall of the adjacent cells of cathode compartment (3) and anolyte compartment (2).
12. according to each reactor (1,13) in the aforementioned claim, the sphericity of wherein said saccharoid (14) is in the 0.6-0.8 scope.
13. according to each reactor (1,13) in the aforementioned claim, the porosity of wherein said towing bed is in the 0.45-0.6 scope, in the preferred 0.50-0.55 scope.
14. in according to aforementioned claim in each the reactor with the method for reduction of continuous or semi-continuous process or oxidation component, wherein carry the catholyte (9) of described component or the lift velocity of anolyte (7) and be chosen as the minimum fluid velocity (υ that determines greater than by following equation
m):
υ
m＝[(ρ
s-ρ
f)gd
p 2]/μ，
Wherein, υ
m=minimum flow velocity, ρ
sThe density of=described saccharoid, ρ
f=described fluidic density, g=universal gravity constant, d
p=median size, μ=fluid viscosity.
15. according to the method for claim 14, wherein said component is vat pigment and/or thioxine dyes, bleaching component in the aqueous solution or the medium that is used for oxidation.
16. according to each method among the claim 14-15, wherein said fluid velocity (υ
m) be adjusted to make at least in the zone of described towing bed laminar flow is arranged, wherein preferred this reaches by selecting following fluid velocity:
υ
m<500μP/S＊(ρ
f)[10(1-ε)/ε
3]。
17. produce subsequently method, wherein according to the towing bed in each the reactor among the claim 1-13 according to each method operation among the claim 14-16
In the first step, the fluid velocity of electrolytic solution increased to and is higher than according to the minimum flow velocity of Stokes equations but is no more than the twice of the minimum value of Stokes equations, and keep at least until the conduction saccharoid (14) that freely suspends pulled recline on grid (11 ');
In second step, flow velocity increased to the minimum value in the following scope
υ
m＝[(ρ
s-ρ
f)gd
p 2]/μ，
Preferably be lower than following value:
υ
m<500μP/S＊(ρ
f)[10(1-ε)/ε
3]
Wherein, for this purpose will with
υ
mc＝[ε
3/{10(1-ε)}]＊υ
m
The flow υ that provides
McIncrease with per second 0.001-0.05cm/s, preferred per second 0.005-0.02cm/s;
The actual electrolytic process of beginning in the 3rd step, wherein the variation of flow velocity keeps low, causes the close mode of described towing bed to avoid described towing bed to reset.
18. be used for the purposes of the vat pigment and/or the sulfur dyeing of fiber, yarn and/or fabric according to each reactor among the claim 1-13, wherein said reactor is used for reducing described dyestuff and/or preparation SYNTHETIC OPTICAL WHITNER and/or dyestuff is being applied to the described dyestuff of rear oxidation on fiber, yarn and/or the fabric, wherein preferably use two independently reactors (25,26), a reactor (25) be used for preparing SYNTHETIC OPTICAL WHITNER and after dyestuff is applied on the fiber the described dyestuff of oxidation, another reactor (26) is used for reducing described dyestuff.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06012925.1 | 2006-06-23 | ||
| EP06012925A EP1870494A1 (en) | 2006-06-23 | 2006-06-23 | Electrochemical reactor |
| PCT/CH2007/000312 WO2007147283A2 (en) | 2006-06-23 | 2007-06-22 | Electrochemical reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101479408A true CN101479408A (en) | 2009-07-08 |
| CN101479408B CN101479408B (en) | 2012-06-27 |
Family
ID=37398679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800236239A Active CN101479408B (en) | 2006-06-23 | 2007-06-22 | Electrochemical reactor |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US8333881B2 (en) |
| EP (2) | EP1870494A1 (en) |
| CN (1) | CN101479408B (en) |
| BR (1) | BRPI0712282B1 (en) |
| CA (1) | CA2654284C (en) |
| ES (1) | ES2572882T3 (en) |
| WO (1) | WO2007147283A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113166954A (en) * | 2018-11-30 | 2021-07-23 | 赛杜工程股份有限公司 | Electrochemical reactor and cleaning or regenerating thereof |
| CN114084937A (en) * | 2021-11-25 | 2022-02-25 | 江苏科技大学 | Ferroelectric chemical water treatment method for convection-enhanced ion mass transfer |
| CN115028242A (en) * | 2021-06-17 | 2022-09-09 | 上海安江环保科技合伙企业(有限合伙) | Electrochemical assembly, device and method for realizing particle confinement |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013191645A1 (en) * | 2012-06-21 | 2013-12-27 | Technodye Dying Colors Pte Ltd | Electrolytic reduction of sulfur dyes |
| US10048233B2 (en) | 2012-11-12 | 2018-08-14 | Dionex Corporation | Suppressor device |
| US9914651B2 (en) | 2013-05-08 | 2018-03-13 | Dionex Corporation | Current efficient electrolytic device and method |
| US9400268B2 (en) | 2014-08-08 | 2016-07-26 | Dionex Corporation | Method for reducing suppressor noise |
| US10107268B1 (en) * | 2014-09-05 | 2018-10-23 | National Technology & Engineering Solutions Of Sandia, Llc | Thermal energy storage and power generation systems and methods |
| US10175211B2 (en) | 2014-12-31 | 2019-01-08 | Dionex Corporation | Current-efficient suppressor and pretreatment device and method |
| JP6395952B1 (en) * | 2016-11-02 | 2018-09-26 | 三菱電機株式会社 | Water treatment apparatus and water treatment method |
| CN113166953A (en) * | 2018-11-30 | 2021-07-23 | 赛杜工程股份有限公司 | Removal of by-products (impurities) |
| US11753730B2 (en) | 2018-11-30 | 2023-09-12 | Sedo Engineering Sa | Leucodye (such as leucoindigo) as dispersing aid |
| WO2020120776A1 (en) * | 2018-12-14 | 2020-06-18 | Redelec Technologie Sa | Electrochemical reactor |
| US11243194B2 (en) | 2019-01-25 | 2022-02-08 | Dionex Corporation | Suppressors with eluent screens for use in ion chromatography |
| US12060678B2 (en) | 2020-01-16 | 2024-08-13 | Indigo Mill Designs, Inc. | Methods and systems to dye textile materials with dye blend compositions having differential dye exhaust rates |
| US20220333253A1 (en) * | 2021-04-08 | 2022-10-20 | Francois Cardarelli | Electrochemical preparation of vanadium electrolytes and sulfates of multivalent transition metals |
| KR102616454B1 (en) * | 2023-03-10 | 2023-12-21 | (주)선유이앤씨 | Hydrogen generating device |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1239983A (en) * | 1968-10-07 | 1971-07-21 | Brown John Constr | Electrochemical processes |
| US3716459A (en) * | 1969-10-16 | 1973-02-13 | Brown John Constr | Electrochemical processes |
| US3966571A (en) * | 1974-04-24 | 1976-06-29 | General Motors Corporation | Method of operating a dynamically packed bed electrode electrochemical cell system |
| US4022678A (en) * | 1975-04-14 | 1977-05-10 | Charles W. Wojcik | Electrolytic cell |
| US4569729A (en) | 1984-07-16 | 1986-02-11 | Chlorine Engineers Corp., Ltd. | Electrolyzing method and electrolytic cell employing fluidized bed |
| US4921587A (en) * | 1985-09-19 | 1990-05-01 | H-D Tech, Inc. | Porous diaphragm for electrochemical cell |
| AT398316B (en) | 1989-06-01 | 1994-11-25 | Verein Zur Foerderung Der Fors | METHOD FOR REDUCING DYE |
| TW251325B (en) | 1993-03-30 | 1995-07-11 | Basf Ag | |
| ATE304075T1 (en) | 1998-11-24 | 2005-09-15 | Walter Marte | METHOD AND APPARATUS FOR THE REDUCTION OF VAK AND SULFUR DYES |
| KR20010106464A (en) * | 1999-07-01 | 2001-11-29 | 추후제출 | Bipolar electrode for electrochemical redox reactions |
| DE19962155A1 (en) | 1999-12-22 | 2001-06-28 | Basf Ag | Electrochemical reduction of vat dye using cathode with electroconductive, cathodically-polarized layer formed in situ by sedimentation on electroconductive substrate, is carried out in presence of base |
-
2006
- 2006-06-23 EP EP06012925A patent/EP1870494A1/en not_active Withdrawn
-
2007
- 2007-06-12 US US12/306,385 patent/US8333881B2/en active Active
- 2007-06-22 BR BRPI0712282-9A patent/BRPI0712282B1/en active IP Right Grant
- 2007-06-22 CN CN2007800236239A patent/CN101479408B/en active Active
- 2007-06-22 EP EP07720209.1A patent/EP2032740B1/en active Active
- 2007-06-22 WO PCT/CH2007/000312 patent/WO2007147283A2/en active Application Filing
- 2007-06-22 ES ES07720209.1T patent/ES2572882T3/en active Active
- 2007-06-22 CA CA2654284A patent/CA2654284C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113166954A (en) * | 2018-11-30 | 2021-07-23 | 赛杜工程股份有限公司 | Electrochemical reactor and cleaning or regenerating thereof |
| CN113166954B (en) * | 2018-11-30 | 2024-07-26 | 赛杜工程股份有限公司 | Electrochemical reactor and its cleaning or regeneration |
| CN115028242A (en) * | 2021-06-17 | 2022-09-09 | 上海安江环保科技合伙企业(有限合伙) | Electrochemical assembly, device and method for realizing particle confinement |
| CN114084937A (en) * | 2021-11-25 | 2022-02-25 | 江苏科技大学 | Ferroelectric chemical water treatment method for convection-enhanced ion mass transfer |
| CN114084937B (en) * | 2021-11-25 | 2024-01-30 | 江苏科技大学 | Ferroelectric chemical water treatment method for convection enhanced ion mass transfer |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007147283A3 (en) | 2008-05-22 |
| EP2032740A2 (en) | 2009-03-11 |
| CA2654284C (en) | 2015-11-24 |
| EP2032740B1 (en) | 2016-02-24 |
| EP1870494A1 (en) | 2007-12-26 |
| CN101479408B (en) | 2012-06-27 |
| BRPI0712282B1 (en) | 2018-06-05 |
| US20090308757A1 (en) | 2009-12-17 |
| ES2572882T3 (en) | 2016-06-02 |
| BRPI0712282A2 (en) | 2012-01-10 |
| WO2007147283A2 (en) | 2007-12-27 |
| CA2654284A1 (en) | 2007-12-27 |
| US8333881B2 (en) | 2012-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101479408B (en) | Electrochemical reactor | |
| CN110038634B (en) | Oxygen evolution reaction catalyst based on MXene and metal organic framework compound composite structure and synthesis method thereof | |
| CN109824185A (en) | A kind of novel three-dimensional electrode water treatment system and graphene conductive particle preparation method | |
| US12104262B2 (en) | Electrochemical reactor and its cleaning or regeneration | |
| CN110479379A (en) | A kind of covalent organic frame material catalyst and its preparation method and application based on load Ru nano particle | |
| CN103255642A (en) | Continuous indigo blue electrochemistry reduction dyeing process | |
| Qin et al. | Promotion of phenol electro-oxidation by oxygen evolution reaction on an active electrode for efficient pollution control and hydrogen evolution | |
| Park et al. | Strategies for CO2 electroreduction in cation exchange membrane electrode assembly | |
| CN103132100B (en) | Technological method for producing pure hydrogen and carbon dioxide from coals | |
| CN1408037A (en) | Electrochemical reduction for reducible dyes | |
| CN202482113U (en) | Three-dimensional electric catalytic water treatment device | |
| CN107720890A (en) | A kind of electro-chemical water processing equipment and method for treating water | |
| Hu et al. | Electrochemical degradation of methylene blue by Pb modified porous SnO2 anode | |
| CN106179410A (en) | A kind of photocatalyst of photocatalytic hydrogen production by water decomposition and preparation method thereof | |
| CN109881213A (en) | A kind of efficient anodic oxidation parity chlorate and cathodic reduction carbon dioxide coupling process | |
| Chai et al. | CO2 utilization and sequestration in Reservoir: Effects and mechanisms of CO2 electrochemical reduction | |
| Gao et al. | Self-sustained recovery of silver with stainless-steel based Cobalt/Molybdenum/Manganese polycrystalline catalytic electrode in bio-electroreduction microbial fuel cell (BEMFC) | |
| CN105363440A (en) | Carbon black loaded hollow platinum-silver-alloy-nanoparticle composite catalyst and preparation method therefor | |
| CN106498437B (en) | A kind of Carbon dioxide electrochemical reduction electrode preparation method | |
| Han et al. | Recent advances in α-Fe2O3-based photocatalysts for CO2 conversion to solar fuels | |
| WO2010094113A1 (en) | Ammonia electrolyzer | |
| CN115261900B (en) | Tubular membrane electrode continuous parallel flow type carbon dioxide reduction electrolytic cell and operation method thereof | |
| CA3119492A1 (en) | Electrochemical reactor | |
| CN116282393A (en) | Palladium-nickel phosphide-foam nickel composite electrode and preparation method and application thereof | |
| CN109092297A (en) | Carbon quantum dot load type palladium nanocomposite and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |